Journal of Molecular Spectroscopy 229 (2005) 145149 www.elsevier.

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Fourier transform infrared emission spectra of MnH and MnD

Iouli E. Gordona, Dominique R.T. Appadoob, Alireza Shayestehb, Kaley A. Walkerb, Peter F. Bernatha,b,*
a b

Department of Physics, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 Department of Chemistry, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 Received 13 April 2004; in revised form 2 August 2004 Available online 25 September 2004

Abstract Fourier transform infrared emission spectra of MnH and MnD were observed in the ground X7R+ electronic state. The vibrationrotation bands from v = 1 0 to v = 3 2 for MnH and from v = 1 0 to v = 4 3 for MnD were recorded at an instrumental resolution of 0.0085 cm1. Spectroscopic constants were determined for each vibrational level and equilibrium constants were found from a Dunham-type t. The equilibrium vibrational constant (xe) for MnH was found to be 1546.84518(65) cm1, the equilibrium rotational constant (Be) is 5.6856789(103) cm1 and the eqilibrium bond distance (re) was determined to be 1.7308601(47) A. 2004 Elsevier Inc. All rights reserved.
Keywords: MnH and MnD; Fourier transform spectrometer; Infrared spectrum; Equilibrium molecular constants

Manganese hydride is one of the most extensively studied high spin molecules. Between 1942 and 1957, Nevin and co-workers [16] recorded and rotationally analyzed the 00 and 01 bands of the A7PX7R+ transition (near 568 and 624 nm) for MnH and MnD. The AX 00 band was later revisited by Varberg et al. [7 9] using laser excitation spectroscopy. They have extended Nevins rotational analysis to the lowest J values for every spin component and studied the nuclear hyperne interaction. Urban and Jones [10,11] observed an infrared spectrum of MnH and MnD using a diode laser spectrometer. They recorded vibrational bands v = 1 0 to v = 3 2, determined equilibrium constants for both molecules and carried out a combined isotopologue t. Unfortunately semiconductor diode lasers cannot cover the whole spectral range of interest. As a result only relatively few infrared lines have been measured; for example only seven R-lines, that are all spin components of a

Corresponding author. Fax: +1 519 746 0435. E-mail address: bernath@uwaterloo.ca (P.F. Bernath).

single R(5) transition, were obtained for the fundamental band of MnH. In this paper, we report new infrared emission spectra of MnH and MnD recorded with a Fourier transform spectrometer. The vibrational bands v = 1 0 to v = 3 2 for MnH and v = 1 0 to v = 4 3 for MnD were observed. Analyses of the new spectra have provided improved ground state molecular constants for MnH and MnD. The same emission source that has proved to be very eective in providing spectra of other metal hydrides in our laboratory was used for MnH and MnD [12,13]. The infrared spectra of MnH/D were recorded between 800 and 1700 cm1 at a resolution of 0.0085 cm1. The recorded infrared emission spectrum of MnH/D contained vibrationrotation bands in the ground electronic 7R+ state. The lines from v = 1 0 to v = 3 2 for MnH and the lines from v = 1 0 to v = 4 3 transitions for MnD were found and analyzed. An overview spectrum of MnD is shown on Fig. 1. To display the bands more clearly the baseline was corrected by eliminating blackbody emission prole using the Bruker OPUS program.

0022-2852/$ - see front matter 2004 Elsevier Inc. All rights reserved. doi:10.1016/j.jms.2004.08.010

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Fig. 1. An overview of the infrared emission spectrum of MnD after baseline correction.

The X7R+ state of MnH obeys Hund case (b) coupling so each rotational level (N) is split into seven spin components (for N P 3) labeled by J with J = N + S, where J is the total angular momentum, N is rotational angular momentum and S is the total electron spin. Examples showing these seven spin components for R(5) and P(7) lines of the fundamental band of MnH are displayed in Fig. 2. The spacing between the spin components in the R branches decreases with increasing of N, causing transitions with N > 20 of fundamental band to be observed as single broad lines. This blending is observed to occur at lower N values as the vibrational quantum number increases. For the v = 4 3 transition in MnD just completely blended R-lines were observed without any trace of corresponding P-lines. The intensities of the spin com-

ponents of each rotational line both in the P- and Rbranches increase from J = N 3 to J = N + 3 as shown in Fig. 2 for R(5) and P(7) transitions of the fundamental band. These line intensities have the classic pattern given by coupling of two angular momenta such as L and S to give J for atoms [14]. Urban and Jones [10] observed deviations from this expected intensity pattern. In the present FT spectrum however this intensity pattern seems to be consistent throughout the spectrum. As an illustration, the lines in Fig. 2 were chosen to be the same as the ones shown in [10]. In our spectrum we were also able to observe a few satellite lines (transitions across spin components) at low N values. The line positions were determined using the program WSpectra [15] written by M. Carleer. The MnH/D spec-

Fig. 2. Example of spin-splitting in MnH lines: R(5) and P(7) transitions of the fundamental band. The intensities of the spin components of each rotational line both in the P- and R-branches increase from J = N 3 to J = N + 3. The spin components are labeled by J values.

I.E. Gordon et al. / Journal of Molecular Spectroscopy 229 (2005) 145149 Table 1 Equilibrium constants (in cm1) for MnH Constant Y1, 0 Y2, 0 Y3, 0 Y0, 1 Y1, 1 104 Y2, 1 104 Y3, 1 104 Y0, 2 106 Y1, 2 107 Y2, 2 107 Y3, 2 109 Y0, 3 109 Y1, 3 1012 Y0, 4 1013 Y1, 4 102 c0, 1 104 c1, 1 105 c2, 1 106 c0, 2 107 c1, 2 103 k0, 0 104 k1, 0 106 k0, 1 This work 1546.84518(65) 27.59744(39) 0.309037(67) 5.6856789(103) 0.1602038(70) 1.200(40) 3.0252(72) 3.05384(58) 1.397(22) 2.823(83) 1.225(16) 9.4670(128) 1.551(48) 1.360(89) 9.16(39) 3.1749( 35) 7.698(54) 4.100(101) 6.763(53) 2.554(98) 3.758(92) 2.623(117) 5.39(43) Ref. [10] 1546.8536(15) 27.60280(91) 0.30822(15) 5.685795(37) 0.160488(22) 0.405(91) 3.255(13) 3.0630(30) 2.983(68) 12.01(16) 8.68(60) 3.2055(83) 8.32(13) 3.40(33) 7.54(21) 3.35(12)a 0.0195(27)a

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components blended into one feature) for MnH and 0.0010.005 cm1 for MnD. Assignments were made for the fundamental band up to N00 = 27 for MnH, for the v = 2 1 transition up to N00 = 24 and for the v = 3 2 transition up to N00 = 21. The corresponding bands of MnD were assigned up to N00 = 37, N00 = 36, and N00 = 33, respectively. While the weak R-branch of the v = 4 3 transition of MnD was followed up to N00 = 29. In total 874 MnH lines and 953 MnD lines were assigned. SPFIT program [16] was used to carry out a Dunham-type t to obtain equilibrium parameters for MnH and MnD using transitions up to v = 3 2. The v = 4 3 band of MnD was excluded because almost all of the observed lines were blended and the inclusion of these transitions led to an unsatisfactory t. In this Dunham-type t each parameter was assumed to have the usual vibrational dependence, X ij X 0j X 1j v 1 X 2j v 1 2 2
2

Numbers in parentheses represent one standard deviation in units of the last digit. a Calculated from values of e0, 1 and e0,2 listed in [10].

tra were calibrated using the line positions of the previous diode laser infrared measurements [10,11]. The eect of blending at higher N values forced us to assign an experimental uncertainty ranging from 0.001 cm1 for strong unblended lines to 0.003 cm1 for completely blended lines (i.e., lines corresponding to seven spin

indicated by rst index for each parameter. The second index for each parameter indicates the order of the rotational dependence. The calculated equilibrium constants are provided in Table 1 for MnH and Table 2 for MnD. Then a t was carried out with SPFIT to determine band constants and the results are presented in Table 3 for MnH and Table 4 for MnD. This time the v = 4 3 band was included for MnD in the t with spinspin and spinrotation constants xed to the values calculated using equilibrium constants from Table 2. No higher order parameters such as h and cs were required to obtain a good t. The diode laser lines of Ur-

Table 2 Equilibrium constants for MnD and BornOppenheimer breakdown parameters estimated using Eq. (2) (in cm1) Constant Y1, 0 Y2, 0 Y3, 0 Y0, 1 Y1, 1 104 Y2, 1 104 Y3, 1 104 Y0, 2 106 Y1,2 107 Y2,2 107 Y3,2 109 Y0,3 109 Y1,3 102 c0,1 104 c1,1 105 c2,1 106 c0,2 103 k0,0 104k1,0 This work 1104.65312(51) 14.22657(31) 0.085848(52) 2.8987214 (57) 0.0581028(33) 1.065(20) 0.4500(35) 0.796939(190) 0.2543(41) 0.521(22) 0.0870(38) 1.5713(197) 0.0957(30) 1.6234(30) 3.026(37) 0.831(99) 1.968(39) 1.823(55) 1.17(11) Ref. [11] 1104.65225(93) 14.22656(54) 0.085813(90) 2.898685(12) 0.0580972(79) 0.943(31) 0.4784(44) 0.79584(54) 0.201(21) 0.897(40) 1.58(12) 1.6388(67) 2.954(76) 2.19(13) 1.44(21)a 1.33(19)a dH l;m dH 1;0 dH 2;0 dH 3;0 dH 0;1 dH 1;1 104 dH 2;1 104 dH 3;1 4 H 10 d0;2 106 dH 1;2 107 dH 2;2 107 dH 3;2 9 H 10 d0;3 109 dH 1;3 1.8268 0.6635 0.14591 0.009919 0.159557 5.8150 1.1914 0.03511 0.048 2.239 0.6059 4.8464 1.0738

Numbers in parentheses represent one standard deviation in units of the last digit. a Calculated from values of a0,1 and a1,1 listed in [11].

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Table 3 Spectroscopic constants (in cm1) for the X7R+ ground state of MnH Constant Tv Bv 104 Dv 109 Hv 1012 Lv cv 106 cDv kv 106 kDv v=0 0 5.6055050(96) 3.04743(57) 8.639(131) 1.861(96) 0.031349( 36) 6.902(58) 0.004020(92) 5.20(46) 0a 5.605746(71) 3.0413(61) 0.030341(82) 11.0(12) 0.00325(10) 0.0 (xed) 1 1490.644889(21) 5.4441092(96) 3.04512(62) 7.532(152) 2.473(122) 0.030497(37) 7.159(64) 0.004230(92) 5.22(49) 2 2923.31542(34) 5.2797006(106) 3.05665(76) 5.926(196) 3.324(174) 0.029559(38) 7.399(71) 0.004462(95) 5.40(55) 3 4296.15620(55) 5.1104876(160) 3.08943(128) 3.38(39) 5.12(39) 0.028548(38) 7.681(80) 0.004778(103) 5.32(60)

Numbers in parentheses represent one standard deviation in units of the last digit. a Constants for v = 0 from [9].

Table 4 Spectroscopic constants (in cm1) for the X7R+ ground state of MnD Constant Tv Bv 105 Dv 109 Hv cv 106 cDv kv v=0 0 2.8696280(55) 7.95559(189) 1.5025(191) 0.0164400(181) 2.418(34) 0.001637(58) 1 1075.920727(133) 2.8111700(52) 7.94459(167) 1.4147(160) 0.0161162(173) 2.410(31) 0.001698(58) 2 2122.616176(206) 2.7520865(50) 7.94981(155) 1.3148(139) 0.0157850(166) 2.396(28) 0.001855(58) 3 3139.57067(27) 2.6921167(51) 7.97910(153) 1.2189(126) 0.0154373(161) 2.403(25) 0.002005(57) 4 4126.0780(25) 2.6310263(193) 8.0685(42) 1.295(27) 0.014704a 1.97a 0.002350a

Numbers in parentheses represent one standard deviation in units of the last digit. a Fixed to the values calculated from Table 2 using Eq. (1).

ban and Jones [10,11] were included in the ts; this was particularly helpful in the case of MnD since the diode laser spectrum was recorded at higher resolution than our Fourier transform measurements and some lines that were blended in our spectrum were resolved. The corresponding lines in our spectrum were given lower weight. Tables 1 and 2 list constants obtained by Urban and Jones [10,11] for comparison. A few lines for certain low N values could not be tted within the experimental uncertainty. This can be attributed to the internal hyperne perturbations discussed by Varberg et al. [9]. Therefore, a larger uncertainty was assigned to those lines. This problem aected most of the observed satellite lines as well, which is particularly disadvantageous since these lines are very useful in determining better values for the spinspin constants. Input and output les of SPFIT program are available on ScienceDirect. The BornOppenheimer breakdown constants were estimated using Le Roys formalism [17]:   l2m=2 MD MH H lMnH MnD MnH Y l;m Y l;m dl;m : 2 MD lMnD The estimated BornOppenheimer breakdown constants dH are given in Table 2. l;m The t of the new and extensive dataset has provided an improved set of constants for the ground states of

MnH and MnD, and allowed to determine higher order expansion constants in the Dunham-type t. The equilibrium bond distance was determined to be 1.7308601(47) A for MnH, based on the value of Be calculated in the t. Our spectroscopic constants for v = 0 can also be compared with those of Varberg et al. [9] in Table 3. Varberg et al. [9] determined a value for h and for cs (a cross-term between spinrotation and spinspin terms) that we nd unnecessary. We nd that the Born Oppenheimer breakdown correction parameters dH l;m are relatively large, as is usually the case for metal hydrides [12].

Acknowledgments Financial support from the Natural Sciences and Engineering Research Council of Canada is gratefully acknowledged.

Appendix. Supplementary material Supplementary data for this article are available on ScienceDirect (www.sciencedirect.com) and as part of the Ohio State University Molecular Spectroscopy Archives (http://msa.lib.ohio-state.edu/jmsa_hp.htm).

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References
[1] T.E. Nevin, Proc. R. Irish Acad. 48 (1942) 145. [2] T.E. Nevin, Proc. R. Irish Acad. 50 (1945) 123137. [3] T.E. Nevin, M. Conway, M. Cranley, Proc. Phys. Soc. A 65 (1952) 115124. [4] T.E. Nevin, P.G. Doyle, Proc. R. Irish Acad. 52 (1948) 35. [5] T.E. Nevin, D.V. Stephens, Proc. R. Irish Acad. 55 (1953) 109. [6] W. Hayes, P.D. McCarvill, T.E. Nevin, Proc. Phys. Soc. A 70 (1957) 904905. [7] T.D. Varberg, R.W. Field, A.J. Merer, J. Chem. Phys. 92 (1990) 71237127. [8] T.D. Varberg, R.W. Field, A.J. Merer, J. Chem. Phys. 95 (1991) 15631576.

[9] T.D. Varberg, J.A. Gray, R.W. Field, A.J. Merer, J. Mol. Spectrosc. 156 (1992) 296318. [10] R.-D. Urban, H. Jones, Chem. Phys. Lett. 163 (1989) 3440. [11] R.-D. Urban, H. Jones, Chem. Phys. Lett. 178 (1991) 295 300. [12] A. Shayesteh, D.R.T. Appadoo, I. Gordon, R.J. Le Roy, P.F. Bernath, J. Chem. Phys. 120 (2004) 1000210008. [13] A. Shayesteh, K. Walker, D.R.T. Appadoo, I. Gordon, P.F. Bernath, J. Mol. Struct. 695 (2004) 2337. [14] E.U. Condon, G. Shortley, The Theory of Atomic Spectra, Cambridge University Press, England, 1951. [15] M. Carleer, Proc. SPIE 4168 (2001) 337. [16] H.M. Pickett, J. Mol. Spectrosc. 148 (1991) 371377. [17] R.J. Le Roy, J. Mol. Spectrosc. 194 (1999) 189196.